Molecular Sieve, COK-5, Its Synthesis and Use

ABSTRACT

A molecular sieve having the structure of COK-5 is produced using, as a structure directing agent, at least one diquaternary ammonium compound selected from the group consisting of 1,4-bis(N-propylpyrrolidinium)butane dications, 1,4-bis(N-butylpyrrolidinium)butane dications and 1,5-bis(N-propylpyrrolidinium)pentane dications.

PRIORITY CLAIM

This application claims the benefits of and priorities to U.S. PatentApplication No. 61/813,940 filed Apr. 19, 2013 and EP Application No.13172271.2 filed Jun. 17, 2013, the disclosures of which areincorporated herein by reference in their entireties.

FIELD

This invention relates to the molecular sieve, COK-5, its synthesis andits use as an adsorbent and as a catalyst for organic conversionreactions.

BACKGROUND

COK-5 is a molecular sieve zeolite characterized by very thin crystalsfrom about 6 to 20 nm in thickness and a distinctive X-ray diffractionpattern which distinguishes it from other known crystalline materials.COK-5 is a highly versatile catalyst useful in a variety of organicconversion reactions.

An example of thin crystal COK-5 and a method of preparation thereof isdisclosed in WO 02/46099-A1, the disclosure of which is incorporated byreference herein in its entirety. WO 02/46099-A1 discloses synthesizingCOK-5 with N,N,N,N′,N′,N′-hexaethylpentane diammonium dibromide (HEPDD)as the structure directing agent:

(C₂H₅)₃N⁺C₅H₁₀N⁺(C₂H₅)₃2Br⁻.

The synthesis further involves a hydrothermal treatment step, which iscarried out under conventional zeolite synthesis conditions, and canextend for as long as 7 to 10 days (see WO 02/46099-A1, Examples 1 and2).

Thus far, HEPDD cations have been identified as the only organiccompound known to direct the synthesis of COK-5. Limited by a singleidentified structure directing agent, the synthesis of COK-5 is acomplex process requiring up to 10 days of heating to obtain a finalproduct, as taught by WO 02/46099-A1. Extensive, prolonged heating andthe absence of alternative structure directing agents (which could alsoexpand the compositional ranges of the zeolite) lead to variousdifficulties and increased costs in the production of COK-5, as well asin catalyst manufacture involving COK-5 zeolitic materials.

Therefore, while HEPDD cations can be used as a structure directingagent for the synthesis of COK-5, a need remains for improved structuredirecting agents, capable of being used in a more simplified synthesisprocess.

According to the present invention, using one or more of1,4-bis(N-propylpyrrolidinium)butane dications,1,4-bis(N-butylpyrrolidinium)butane dications and1,5-bis(N-propylpyrrolidinium)pentane dications as a structure directingagent, it has now been found that COK-5 can be synthesized by simplerprocesses and in shorter heating periods than was previously possibleusing HEPDD as the structure directing agent. Using these new directingagents, COK-5 can be made across a wide range of Si/Al and Si/B atomicratios under typical OH/SiO₂ molar ratios in sodium, potassium, orlithium-containing gels. In addition, it is possible to produce COK-5with extremely small crystal size resulting in a material having aunique powder X-ray diffraction (XRD) pattern.

SUMMARY

In one aspect, the invention resides in a molecular sieve having thestructure of COK-5 and comprising in its pores at least one diquaternaryammonium compound selected from 1,4-bis(N-propylpyrrolidinium)butanedications, 1,4-bis(N-butylpyrrolidinium)butane dications and1,5-bis(N-propylpyrrolidinium)pentane dications.

In one embodiment, the molecular sieve has a composition comprising themolar relationship:

mQ:(n)YO₂:X₂O₃

wherein 0<m/n≤0.2, n is at least 20, 0<m≤0.2n, Q is said at least onediquaternary ammonium compound, X is a trivalent element, such asaluminum or boron, and Y is a tetravalent element, such as silicon.

Conveniently, the molecular sieve comprises crystals having an externalsurface area of about 100 to about 300 m²/g and a total surface area ofabout 350 to about 650 m²/g, both as determined by the t-plot method fornitrogen physisorption.

In another aspect, the invention resides in a molecular sieve having thestructure of COK-5 and having an X-ray diffraction pattern with a firstcomposite peak with a maximum at 25.0 (±0.30) degrees 2-theta (2θ) whichhas an intensity above background of Imax_(A) and which intersects asecond composite peak with a maximum at 23.0 (±0.20) degrees 2-theta(2θ) to form a local minimum which has an intensity above background ofImin_(A), such that the Imin_(A)/Imax_(A) ratio is >0.7.

In yet another aspect, the invention resides in a molecular sieve havingthe structure of COK-5 and comprising crystals having an externalsurface area of at least 100 m²/g as determined by the t-plot method fornitrogen physisorption and having an X-ray diffraction pattern with asingle diffuse composite feature in the 2-theta (2θ) range from 21.5 to25.5 degrees.

In further aspect, the invention resides in a process for producing amolecular sieve having the structure of COK-5, the process comprising:

(i) preparing a synthesis mixture capable of forming said molecularsieve, said mixture comprising a source of an alkali metal (M), a sourceof an oxide of a tetravalent element (Y), a source of a trivalentelement (X), water, and a directing agent (Q) comprising one or more of1,4-bis(N-propylpyrrolidinium)butane dications,1,4-bis(N-butylpyrrolidinium)butane dications and1,5-bis(N-propylpyrrolidinium)pentane dications, and said mixture havinga composition, in terms of mole ratios, within the following ranges:

YO₂/X₂O₃ at least 20;

H₂O/YO₂ about 20 to about 60;

M/YO₂ about 0.1 to about 0.5;

OH⁻/YO₂ about 0.2 to about 0.6; and

Q/YO₂ about 0.04 to about 0.25;

(ii) heating said mixture under crystallization conditions including atemperature of from about 125° C. to about 200° C. until crystals ofsaid molecular sieve are formed; and

(iii) recovering said molecular sieve from step (ii).

In yet further aspect, the invention resides in a process for convertinga feedstock comprising an organic compound to a conversion product whichcomprises contacting said feedstock at organic compound conversionconditions with a catalyst comprising an active form of the molecularsieve described herein.

In still yet further aspect, the invention resides in a1,4-bis(N-propylpyrrolidinium)butane compound having the followingformula:

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 compares the 20 to 30 degree two theta region of the X-raydiffraction pattern of a conventional COK-5 product with the same regionof the X-ray diffraction pattern of a small crystal COK-5 producedaccording to the present invention.

FIG. 2 shows the X-ray diffraction patterns of the as-synthesizedproducts of Example 1 after crystallization for 3 days and 6 days.

FIG. 3 shows the X-ray diffraction patterns of the as-synthesized(as-made) and as-calcined products of Example 2.

FIG. 4 shows scanning electron micrograph (SEM) images of theas-synthesized product of Example 2.

FIG. 5 shows the X-ray diffraction patterns of the as-synthesizedproducts of Example 4 after crystallization for 10 days and 12 days.

FIG. 6 shows the X-ray diffraction patterns of the as-synthesizedproduct of Example 5.

FIG. 7 shows the X-ray diffraction patterns of the as-synthesizedproducts of Example 6 after crystallization for 7 days and 9 days.

FIG. 8 shows scanning electron micrograph (SEM) images of theas-synthesized product of Example 6 after crystallization for 9 days.

FIG. 9 shows the X-ray diffraction patterns of the as-synthesizedproduct of Example 7.

FIG. 10 shows scanning electron micrograph (SEM) images of theas-synthesized product of Example 7.

FIG. 11 shows the X-ray diffraction patterns of the as-synthesizedproduct of Example 8.

FIG. 12 shows scanning electron micrograph (SEM) images of theas-synthesized product of Example 8.

FIG. 13 compares the X-ray diffraction patterns of the as-synthesizedproducts of Example 9 after crystallization for 13 days and 15 days withthat of conventional COK-5.

FIG. 14 shows SEM images of the 13-day product of Example 9.

FIG. 15 shows TEM images of the 13-day product of Example 9.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Described herein is a process for the synthesis of the zeolite, COK-5,using as a structure directing agent one or more of the diquaternaryammonium compounds selected from the group consisting of1,4-bis(N-propylpyrrolidinium)butane dications,1,4-bis(N-butylpyrrolidinium)butane dications and1,5-bis(N-propylpyrrolidinium)pentane dications. By using thesedirecting agents, it is found that COK-5, with a broader range ofcompositions (range of silica to alumina molar ratios and borosilicatecompositions) and smaller crystal size, can be obtained as compared tousing the HEPDD cations previously employed to produce COK-5.

Also described is a new ultra-small crystal form of COK-5 which exhibitsa unique X-ray diffraction pattern.

As conventionally synthesized, zeolite COK-5 is characterized by anX-ray diffraction pattern (XRD) which has, as the only sharp peaks inthe degrees 2 theta (2θ) (Cu K-α) region extending from 5 to 25.5degrees, four sharp peaks at degrees 2 theta (2θ) values of 8.82±0.1,12.44±0.1, 23.01±0.1 and 25.02±0.1 degrees. Although these are the onlysharp peaks in the degrees 2 theta (2θ) (Cu K-α) region extending from 5to 25.5 degrees 2-theta (2θ), most samples of the zeolite exhibit anumber of unresolved broad peaks such that the overall XRD pattern ofCOK-5 may be summarized as set out in Table 1.

TABLE 1 Two Theta (2θ), degrees Intensity Nature of Peak   6 to 8.7 W/MUnresolved series of broad peaks 8.82 ± 0.1 S Sharp peak 12.44 ± 0.1  MSharp peak  14 to 16 M Unresolved series of broad peaks  20.4 to 21.2 WBroad peak 23.01 ± 0.1  VS Sharp peak  22.5 to 24.5 M/S Unresolvedseries of broad peaks 25.02 ± 0.1  S Sharp peak 25.5 to 27  M Unresolvedseries of broad peaks

It is known that certain lines in the X-ray patterns of zeolites tend tobroaden as the crystal size of the relevant zeolite decreases so thatadjacent lines may begin to overlap and thereby appear as only partiallyresolved peaks or as unresolved broad peaks. In certain embodiments ofthe COK-5 described herein, this line broadening results in there beingonly a diffuse composite peak in the 2-theta (2θ) range from about 21.5to 25.5 degrees 2-theta (2θ) (CuKα) of the X-ray pattern. In such cases,the maximum of the composite peak near 25.0 (±0.1) degrees 2-theta (2θ)either appears as a shoulder or forms part of a large diffuse compositefeature with the peak with maximum near 23.0 (±0.1) degrees 2-theta(2θ). In a powder XRD pattern of a typical (larger crystallite) COK-5sample, the composite peak with a maximum near 23.0 degrees 2-theta (2θ)and the composite peak near 25.0 degrees 2-theta (2θ) will intersect toform a clearly visible local minimum [see FIG. 1(a)]. In these typicalpreparations, the ratio of the relative background-subtracted intensityof this local minimum to the relative background-subtracted intensity ofthe composite peak near 25.0 degrees 2-theta (2θ) will be less than 0.5in both the as-made and calcined forms of the zeolite. In one embodimentof the small crystal preparations described herein, the local minimummay be clearly discerned from the composite peak near 25.0 degrees2-theta (2θ) but this ratio will be greater than 0.70. In anotherembodiment, the crystals become so small and the peaks are so severelybroadened that the peak maximum near 25.0 degrees 2-theta (2θ) eitherappears as an inflection point of the large diffuse composite peak witha maximum near 23.0 (±0.20) degrees 2-theta (2θ) or no local maximum orinflection point is discerned for the composite peak near 25.0 (±0.30)degrees 2-theta (2θ) [see FIG. 1(b) and FIG. 1(c)].

It will be appreciated that, with the ultra-small crystal embodimentsdescribed above, X-ray diffraction alone may not be sufficient toidentify the material as having the COK-5 structure, in which case otheranalytical methods, such as high resolution transmission electronmicroscopy and electron diffraction, may be necessary to confirm theidentity of the material as COK-5.

The X-ray diffraction data reported herein were collected with aPanalytical X'Pert Pro diffraction system with an Xceleratormultichannel detector, equipped with a germanium solid state detector,using copper K-alpha radiation. The diffraction data were recorded bystep-scanning at 0.02 degrees of two-theta, where theta is the Braggangle, and an effective counting time of 2 seconds for each step. Theinterplanar spacings, d-spacings, were calculated in Angstrom units, andthe relative intensities of the lines, I/I_(o) is one-hundredth of theabsolute intensity of the strongest line, above background. Theintensities are uncorrected for Lorentz and polarization effects. Therelative intensities are given in terms of the symbols vs=very strong(75-100), s=strong (50-74), m=medium (25-49) and w=weak (0-24).

In its as-synthesized form, the COK-5 described herein has a compositioncomprising the molar relationship:

mQ:(n)YO₂:X₂O₃,

wherein 0<m/n≤0.2, n is at least 20, 0<m≤0.2n, Q is said at least onediquaternary ammonium compound selected from1,4-bis(N-propylpyrrolidinium)butane dications,1,4-bis(N-butylpyrrolidinium)butane dications and1,5-bis(N-propylpyrrolidinium)pentane dications, X is a trivalentelement, such as boron or aluminum, and Y is a tetravalent element, suchas silicon.

The COK-5 described herein is produced from a synthesis mixturecomprising a source of an alkali metal (M), a source of an oxide of atetravalent element (Y), a source of a trivalent element (X), water, anda directing agent (Q) comprising one or more of1,4-bis(N-propylpyrrolidinium)butane dications,1,4-bis(N-butylpyrrolidinium)butane dications and1,5-bis(N-propylpyrrolidinium)pentane dications, wherein the mixture hasa composition, in terms of mole ratios, within the following ranges:

Reactants Useful Preferred YO₂/X₂O₃  20 to 200  24 to 100 H₂O/YO₂ 15 to60 20 to 45 OH⁻/YO₂ 0.2 to 0.6 0.3 to 0.5 Q/YO₂ 0.04 to 0.5  0.05 to0.2 

The alkali metal (M) is generally potassium, sodium or lithium and asuitable source of the alkali metal is the hydroxide.

Suitable sources of the trivalent element X depend on the element Xselected but, in one preferred embodiment, in which the element X isaluminum or boron, suitable sources of aluminum include hydrated aluminaand fumed alumina and water-soluble aluminum salts, such as aluminumnitrate. Suitable sources of boron include boric acid and water-solubleborate salts, such as sodium borate.

Suitable sources of the tetravalent element Y depend on the element Yselected but, in one preferred embodiment, in which Y is silicon,include colloidal suspensions of silica, precipitated silica, alkalimetal silicates, tetraalkyl orthosilicates, and fumed silicas.

Combined sources of two or more of the components M, X and Y can also beused as sodium aluminate and metakaolin.

Suitable sources of the directing agent Q include the hydroxides and/orsalts of the relevant quaternary ammonium compounds.1,4-bis(N-propylpyrrolidinium)butane and1,5-bis(N-propylpyrrolidinium)pentane compounds can be readilysynthesized by the reaction of N-propylpyrrolidine with1,4-dibromobutane and 1,5-dibromopentane, respectively. Similarly,1,4-bis(N-butylpyrrolidinium)butane compounds can be readily synthesizedby the reaction of N-butylpyrrolidine with 1,4-dibromobutane.N-propylpyrrolidine and N-butylpyrrolidine are known materials but canbe synthesized by reaction of pyrrolidine with 1-iodopropane and1-iodobutane, respectively, or by reductive amination of propionaldehydeor butyraldehyde with pyrrolidine.

Crystallization of COK-5 from the above synthesis mixture can be carriedout at either static or stirred conditions in a suitable reactor vessel,such as for example, polypropylene jars or teflon lined or stainlesssteel autoclaves, at a temperature of about 125° C. to about 200° C. fora time sufficient for crystallization to occur at the temperature used,e.g., at least 1 day, such as from about 1 to about 21 days. Thereafter,the crystals are separated from the liquid and recovered.

The synthesis may be aided by seeds from a previous synthesis of COK-5,with the seeds suitably being present in an amount of from about 0.01ppm by weight to about 10,000 ppm by weight, such as from about 100 ppmby weight to about 5,000 ppm by weight of the synthesis mixture.

To the extent desired and depending on the X₂O₃/YO₂ molar ratio of thematerial, any alkali or alkaline earth metal cations in theas-synthesized COK-5 can be replaced in accordance with techniques wellknown in the art by ion exchange with other cations. Preferred replacingcations include metal ions, hydrogen ions, hydrogen precursor, e.g.,ammonium ions and mixtures thereof. Particularly preferred cations arethose which tailor the catalytic activity for certain hydrocarbonconversion reactions. These include hydrogen, rare earth metals andmetals of Groups 2 to 15 of the Periodic Table of the Elements. As usedherein, the numbering scheme for the Periodic Table Groups is asdisclosed in Chemical and Engineering News, 63(5), 27 (1985).

The as-synthesized COK-5 may also be subjected to treatment to removepart or all of the organic directing agent Q used in its synthesis. Thisis conveniently effected by thermal treatment in which theas-synthesized material is heated at a temperature of at least about370° C. for at least 1 minute and generally not longer than 20 hours.While subatmospheric pressure can be employed for the thermal treatment,atmospheric pressure is desired for reasons of convenience. The thermaltreatment can be performed at a temperature up to about 925° C.Alternatively, the organic directing agent Q can be removed by treatmentwith ozone (see, e.g., Parikh et al., Microporous and MesoporousMaterials 76 (2004) pp. 17-22).

The COK-5 molecular sieve produced by the present process forms asflake-like crystals. Depending on their size, the crystals may have anexternal surface area of at least 100 m²/g, such as about 100 to about300 m²/g and a total surface area of at least 350 m²/g, such as about350 to about 650 m²/g. All surface area values given herein aredetermined from nitrogen physisorption data using the t-plot method.Details of this method can be found in Lippens, B. C. and deBoer, J. H.,“Studies on pore systems in catalysts: V. The t method”, J. Catal., 4,319 (1965), the entire contents of which are incorporated herein byreference.

The COK-5 produced by the present process, if required after cationexchange and/or calcining, has utility as a catalyst or catalystprecursor and as a separation and absorption medium. The material isespecially useful in numerous hydrocarbon conversions, separations andadsorptions. It may be used alone, or in admixture with other molecularsieves, in particulate form, supported or unsupported, or in the form ofa supported layer. Hydrocarbon conversions include, for example,cracking, reforming, hydrofining, aromatization, oligomerization (e.g.,di- and trimerization, especially of olefins having 3 to 6 carbon atoms,more particularly butene trimerization), isomerization, dewaxing, andhydrocracking (e.g., naphtha to light olefins, higher to lower molecularweight hydrocarbons, alkylation, transalkylation, disproportionation orisomerization of aromatics). Other conversions include the reaction ofalcohols with olefins and the conversion of oxygenates to hydrocarbons.

The invention will now be more particularly described with reference tothe following non-limiting Examples and the accompanying drawings.

Example 1: COK-5 Synthesis with 1,4-bis(N-butylpyrrolidinium)butaneCations

1,4-bis(N-butylpyrrolidinium)butane cations were prepared by adding 50 gN-butylpyrrolidine (0.39 mol, Aldrich) to 170 mL acetonitrile in a3-necked round bottom flask. Next 36.7 g 1,4-dibromobutane (0.17 mol)was added dropwise with stirring. The reaction was then refluxed for 5hours. The precipitated solids were then filtered with a Buchner funnel,washed with acetone, washed with ether, and then allowed to dry. ¹H NMRshowed the compound to be pure. The dibromide salt was thenion-exchanged into the hydroxide form by dissolving in water and passingit through a column of Dowex LC NG hydroxide exchange resin. Theconcentration of the aqueous solution was determined by titration with astandard solution of 0.1 N HCl.

A gel was prepared by mixing 3.45 g of the1,4-bis(N-butylpyrrolidinium)butane diquat solution ([OH]=0.87 mmol/g)with 2.63 g 1 N KOH and 0.94 g deionized water inside a Teflon liner fora 23-mL steel Parr autoclave. 0.085 g fumed alumina was then mixed withthe solution to create a uniform suspension. 2.25 g Ludox AS-40 was thenmixed with the suspension to form a gel having the followingcomposition: Si/Al=9, the total OH/SiO₂=0.375, and KOH/SiO₂=0.175.

The liner was then capped, sealed inside a 23-mL autoclave, and heatedat 160° C. under tumbling conditions (˜50 rpm). The solids were thenisolated by filtering through a Buchner funnel, washing with deionizedwater, and drying in a vacuum oven at 60° C. FIG. 2 shows the powderdiffraction patterns of samples obtained after 3 and 6 days of heating.The powder diffraction pattern of the 3-day timepoint matches that ofthe COK-5. After a few days of additional heating, there are additionalpeaks around 26-28 degrees 2 theta (2θ) that are due to sanidine, adense phase potassium aluminosilicate.

Similar preparations using alumina trihydrate as the Al source were alsofound to produce COK-5.

Example 2: COK-5 Synthesis with 1,4-bis(N-butylpyrrolidinium)butaneCations

Example 1 was repeated with less (⅔) aluminum so that the gelSi/Al=13.5. After 3 days, a product with a clean diffraction pattern wasobtained. X-ray diffraction patterns for the as-synthesized andas-calcined products are shown in FIG. 3, while FIG. 4 shows SEM imagesof the as-synthesized product. The zeolite was heated inside a mufflefurnace from ambient temperature to 400° C. at 4° C./min under anitrogen atmosphere, then heated to 600° C. at 4° C./min in air, andmaintained at 600° C. in air for 2 hours. After calcination, the samplewas ammonium-exchanged in a solution created by dissolving an equal massammonium nitrate (to that of the zeolite) in a 10-fold mass of thezeolite. The zeolite/ammonium nitrate suspension was heated overnight ina steambox at 98° C. The zeolite was then isolated by filtration, washedthoroughly with deionized water, and allowed to dry overnight in avacuum oven at 60° C. The zeolite was then calcined to 500° C. toconvert it to the acidic form. The surface area of the sample was thenmeasured using nitrogen physisorption and the data were analyzed withthe t-plot method. The determined internal micropore surface area is 270m²/g and the external surface area is 196 m²/g (total surface area of466 m²/g).

Example 3: COK-5 Synthesis with 1,4-bis(N-propylpyrrolidinium)butaneCations

N-propylpyrrolidine was prepared by adding 75.0 g pyrrolidine (1.06 mol)to 300 mL methanol in a round-bottom flask. 206.5 g 1-iodopropane (1.21mol) was then added dropwise with stirring. The mixture was thenrefluxed for 1 hour. The methanol was then removed under vacuum in arotary evaporator, and then 100 mL deionized water was added to theliquid residue. The aqueous mixture was then extracted with ether toremove unreacted 1-iodopropane. 77.30 g KOH was then dissolved in 100 mLdeionized water; this basic solution was then added to the aqueousfraction (the reason for this step is that most of the product is in theform a hydrohalide salt; the base neutralizes the HI component and freesthe amine so that it can be more easily isolated from the aqueousfraction). The mixture was then extracted with ether, and the ethylether was removed under vacuum by rotary evaporation to yield 97%N-propylpyrrolidine (the other 3% was ether as inferred from ¹H NMR).

The diquat was then formed by adding 25.0 g of the 97%N-propylpyrrolidine (0.21 mol) to 60 mL acetonitrile inside a Teflonliner for a 125-mL steel Parr autoclave. Next 21.0 g 1,4-dibrombutane(0.097 mol) was added to the mixture. The 125-mL Teflon liner wascapped, sealed inside the Parr autoclave, and then heated at 80° C. for4 days. The precipitated solids were then filtered, washed with acetone,washed with ethyl ether, and then allowed to dry. The total mass ofclean product (by ¹H and ¹³C NMR) was 42.6 g (97% yield). The dibromidesalt was then ion-exchanged into the hydroxide form by dissolving inwater and passing it through a column of Dowex LC NG hydroxide exchangeresin. The concentration of the aqueous solution was determined bytitration with a standard solution of 0.1 N HCl.

The resultant diquat solution was used in a plurality of parallel smallscale (1 ml) synthesis reactions using gels having compositions withSi/Al,B=100 to 20 under typical OH/SiO₂ molar ratios and containingsodium, potassium, or lithium cations. Aluminum nitrate was used as theAl source and boric acid was used as the B source. Details of thesynthesis reactions are given in Table 2, where Q refers to the1,4-bis(N-propylpyrrolidinium)butane diquat and T refers to the T-atom,and where the ratios in column 2 are expressed as atomic ratios and theratios in columns 3, 4 and 5 are expressed as molar ratios.

TABLE 2 Free Temp ° C., Run T³⁺, Si/T³⁺ M, MOH/SiO₂ Q/Si OH/SiO₂* Time AAl, 40 Na, 0.30 0.15 0.30 160° C., 4 days B Al, 100 Na, 0.30 0.10 0.20160° C., 4 days C B, 100 K, 0.15 0.15 0.30 160° C., 7 days D Al, 40 Na,0.30 0.19 0.60 160° C., 7 days E Al, 40 Na = Li, 0.30 0.19 0.60 160° C.,7 days F Al, 20 K, 0.30 0.23 0.60 160° C., 7 days G Al, 20 Na = Li, 0.300.23 0.60 160° C., 7 days H B, 40 Li, 0.30 0.15 0.60 160° C., 4 days IAl, 40 Na, 0.15 0.15 0.30 160° C., 7 days J Al, 40 Na, 0.30 0.15 0.30160° C., 7 days K B, 20 Na, 0.30 0.15 0.30 160° C., 7 days L Al, 40 Na,0.30 0.15 0.40 160° C., 7 days *Free OH/SiO₂ accounts for neutralizationof hydroxide by aluminum sources and by addition of HCl to bring theconcentration to the specified OH/SiO₂ molar ratio.

Each of the synthesis reactions produced COK-5, in some cases in timesas short as 4 days. In fact, the 1,4-bis(N-propylpyrrolidinium)butanediquat was found to be remarkably selective for the synthesis of COK-5.

Example 4: COK-5 Synthesis with 1,4-bis(N-butylpyrrolidinium)butaneCations

3.45 g of an aqueous solution of 1,4-(N-butylpyrrolidinium)butanehydroxide ([OH]=0.87 mmol/g) was mixed with 2.63 g 1 N KOH and 0.94 gdeionized water inside a 23-mL Teflon insert for a steel Parr autoclave.Next 0.06 g fumed alumina (Cabot) was added to the solution. The linerwas then capped and sealed within a steel Parr autoclave and heated at160° C. under tumbling conditions for 1 hour. The autoclave was thenremoved and allowed to cool to ambient temperature. The autoclave wasthen opened and 2.25 g Ludox AS-40 was added to the mixture. The Teflonliner was then capped and sealed the steel autoclave. The autoclave wasthen placed in an oven at 160° C. under tumbling conditions (50 rpm).FIG. 5 shows the powder XRD of the solid products after 10 and 12 daysof heating. ICP of the 10-day product showed the material to have aSi/Al ratio of 12.3. ²⁷Al NMR of the 12-day product shows that thealuminum in the final product is tetrahedral.

Example 5: COK-5 Synthesis with 1,4-bis(N-butylpyrrolidinium)butaneCations

3.45 g of an aqueous solution of 1,4-(N-butylpyrrolidinium)butanehydroxide ([OH]=0.87 mmol/g) was mixed with 2.63 g 1 N KOH and 2.93 gdeionized water inside a 23-mL Teflon insert for a steel Parr autoclave.Next 2.08 g Ludox AS-40 (40% silica) and 0.13 g metakaolin were added tothe solution. The Teflon liner was then capped and sealed within a 23-mLParr steel autoclave. The autoclave was then placed in a spit within anoven at 160° C. under tumbling conditions (50 rpm) for 3 days. PowderXRD (FIG. 6) of the resulting solid product showed it to be pure COK-5.

Example 6: COK-5 Synthesis with 1,4-bis(N-butylpyrrolidinium)butaneCations

Example 5 was repeated except the synthesis was performed at 140° C. andthe reaction was sampled after 7 and 9 days. FIG. 7 provides the powderXRD patterns of the COK-5 products and shows some peak broadening ascompared with the product of Example 5. FIG. 8 shows SEM images of the9-day product.

Example 7: COK-5 Synthesis with 1,4-bis(N-butylpyrrolidinium)butaneCations

31.80 g of an aqueous solution of 1,4-(N-butylpyrrolidinium)butanehydroxide ([OH]=0.86 mmol/g) was mixed with 23.96 g 1 N KOH and 8.2 gdeionized water inside an 125-mL Teflon insert for a steel Parrautoclave. Next 0.55 g fumed alumina (Cabot) was added to the solution.The liner was then capped and sealed within a steel Parr autoclave andheated at 150° C. under tumbling conditions for 1 hour. The autoclavewas then removed and allowed to cool to ambient temperature. Theautoclave was then opened and 20.5 g Ludox AS-40 was added to themixture. The Teflon liner was then capped and sealed within the steelautoclave. The autoclave was then placed in a spit within an oven at150° C. under tumbling conditions (30 rpm) for 9 days. FIG. 9 shows thepowder XRD of the COK-5 product and FIG. 10 shows the corresponding SEMimages.

Example 8: COK-5 Synthesis with 1,4-bis(N-butylpyrrolidinium)butaneCations

23.96 g 1 N KOH and 8.57 g deionized water were mixed inside an 125-mLTeflon insert for a steel Parr autoclave. Next 0.55 g fumed alumina(Cabot) was added to the solution. The liner was then capped and sealedwithin a steel Parr autoclave and heated at 160° C. under tumblingconditions for 30 minutes. The autoclave was then removed and allowed tocool to ambient temperature. The autoclave was then opened and 31.43 gof an aqueous solution of 1,4-(N-butylpyrrolidinium)butane hydroxide([OH]=0.87 mmol/g) was added to the suspension. The Teflon liner wasthen capped and sealed inside the autoclave. The autoclave was thenplaced in a spit within an oven at 160° C. under tumbling conditions for40 minutes. The autoclave was then removed and allowed to cool toambient temperature. The autoclave was opened and 20.5 g Ludox AS-40 wasadded to the mixture. The Teflon liner was then capped and sealed in thesteel autoclave. The autoclave was then placed in a spit within an ovenat 160° C. under tumbling conditions (30 rpm) for 7 days. FIG. 11 showsthe powder XRD of the COK-5 product and FIG. 12 shows the correspondingSEM images.

Example 9: COK-5 Synthesis with 1,4-bis(N-butylpyrrolidinium)butaneCations

Example 2 was repeated except that the fumed alumina was pre-dissolvedin the hydroxide sources before the addition of the Ludox AS-40. Thepre-dissolution was carried out in a similar manner to that described inExample 7. The crystallization was significantly slower when thealuminum was completely dissolved; requiring 13 days (instead of 3) toobtain the product with the powder XRD pattern shown at the bottom ofFIG. 13. The middle trace shows the powder diffraction pattern after 15days, and the top trace shows the powder pattern of a typical sample ofCOK-5. FIG. 14 shows SEM images of the 13-day product, while FIG. 15shows TEM images of the same product. TEM shows that the lengths of thecrystals are generally between 10 and 50 nm and the widths of thecrystals are generally 4-10 nm in size. After the crystals aremicrotomed and examined by TEM, it is found that the crystals aregenerally about 4 nm in thickness. ²⁷Al MAS NMR indicates that all ofthe aluminum in both the 13-day product and the 15-day product is in atetrahedral coordination.

The 15-day product was then calcined in a muffle furnace by heating in anitrogen stream from ambient temperature to 400° C. over a two hourperiod, maintaining this temperature for 15 minutes, switching the gasstream to air, increasing the temperature from 400° C. to 600° C. over atwo hour period, maintaining the temperature at 600° C. for 2 hours, andthen allowing the furnace to cool to ambient conditions. Aftercalcination, the sample was ammonium-exchanged in a solution created bydissolving an equal mass ammonium nitrate (to that of the zeolite) in a10-fold mass of the zeolite. The zeolite/ammonium nitrate suspension washeated overnight in a steambox at 98° C. The zeolite was then isolatedby filtration, washed thoroughly with deionized water, and allowed todry overnight in a vacuum oven at 60° C. The zeolite was then calcinedto 500° C. to convert it to the acidic form. The surface area of thesample was then measured using nitrogen physisorption. Analysis of thephysisorption data by the t-plot method shows that this materialpossesses an external surface area of 314 m²/g and an internal surfacearea of 314 m²/g (0.135 cc/g micropore volume), i.e., for this samplehalf of the measured surface area is due to the external surface of thecrystallites.

All patents, test procedures, and other documents cited herein,including priority documents, are fully incorporated by reference to theextent such disclosure is not inconsistent and for all jurisdictions inwhich such incorporation is permitted.

While the illustrative forms disclosed herein have been described withparticularity, it will be understood that various other modificationswill be apparent to and can be readily made by those skilled in the artwithout departing from the spirit and scope of the disclosure.Accordingly, it is not intended that the scope of the claims appendedhereto be limited to the examples and descriptions set forth herein butrather that the claims be construed as encompassing all the features ofpatentable novelty which reside herein, including all features whichwould be treated as equivalents thereof by those skilled in the art towhich this disclosure pertains.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.The term “comprising” is synonymous with the term “including”. Likewisewhenever a composition, an element or a group of components is precededwith the transitional phrase “comprising”, it is understood that we alsocontemplate the same composition or group of components withtransitional phrases “consisting essentially of”, “consisting of”,“selected from the group of consisting of”, or “is” preceding therecitation of the composition, component, or components, and vice versa.

1-13. (canceled)
 14. An organic nitrogen compound comprising a dicationhaving the following formula: